N, n&#39;-phthalyl hydrazine fungicidal composition



Patented Oct. 6, 1953 N ,N-PHTHA-IJYL HYDRAZIN E FUN GICIDAL GOMPOSITIQNWaldo ,Ligett, Ponti c, Box .1) olosson, {De roit and Calvin N. Wolf,Fernda'le, to Ethyl Co p at o ew York, pcration of Delaware No Drawing.original application Qotober :28,

nd thi 1.950, Serial No.- 192, p ication January 3 (ll-aims.

This invention has for its object the production of a new group ofsuperior fungitoxic materials, and methods for their use in protectingagricultural, organic and related articles from attack by fungi. Thisapplication is a division of .co-pendi-ng application Serial No. 192,804filed October 28, 19.50, now abandoned.

We have found that N,N-phthalylhydrazine and salts thereof possessunusual fungicidal properties. Alone, these materials are too powerfulfor safe application, but when suitably diluted and formulated ashereinafter described they are excellent fungicides. Such diluentsfunction as surface-contacting a ents and extenders.

By the term fungicide we mean to include not only the property ofdestroying fungi, but also the property of inhibiting the germination ofthe spores of the fungi.

One method of applying ,N,N'ephthalylhydra Zinc and its salts is in theform of a water suspension, wherein a surface active agent has beenincorporated in sufficient amount to disperse and suspend the fungicide.Examples of such surface active agents which can he employed in formingdispersions of our fungicides include salts of the alkyl and alkylarylsulfonates, such as du Pont MP-l89 and Nacconol-NR, alkyl sulfates, suchas Dref-t, alkylamide sulfonates, such as Igepon-T, the alkylarylpolyether alcohols,

such as Triton .X-lOO, the fatty acid esters of polyhydri-e alcohols,such as span, the ethylene oxide addition products of such esters, asfor-example Tween, and the addition products of longchain mercaptans andethylene oxide, such as Sharples Non-Ionic-218. active agents can beemployed, the above merely constituting a representative list of themore common materials.

The solubility of .N,N-phthalylhydrazine in organic solvents is suchthat it can .be applied advantageously in the form of solutions in thistype of solvent, and for certain applications this method of applicationis preferred. For example, in treating cloth, leather, fur, felting orother fibrous articles it may be desirable to apply our fungicidesdissolved in a volatile solvent. After use the volatile solventevaporates leaving the fungicide impregnated throughout the surface ofthe article. Likewise, in applying our fungicides to smooth surfaces, asfor examp e in treati Still other surface 804-v illividedhl 0, 1952,Serial No. 359,126

wood surfaces for protection against fun us al tack, a solution ma bethe most practical method for applying a protective film by brushing,spraying or dipping. The choice of an appropriate solvent is determinedlargely by the concentration of active ingredient which it is desired top by t olatility required in a solvent. the spreading or flowcharacteristics thereof, and by the nature of the material beingtreated. Among the many organic solvents which can be employed as thecarrier for our fungicides we can employ hydrocarbons, such asikerosene, benzene or toluene; ketones, such as acetone and ,me'thy'hethyl ketone; chlorinated solvents, such as carbon tetrachloride,trichloroand perchloro-ethylene: and esters, such as ethyl, butyl andamyl acetates; and alcohols, such as methanol, ethanol and isopropanol.Among the solvents which we prefer to employ are the Carloitols andCellosolves, the former comprising in general the monoalkyl others ofdiethylene glycol and the latter the monoalkyl others of ethyleneglycol. .In addition. combinations of these various typical solvents canbe employed whereby special volatility and viscosity characteristics canbe imparted to our formulations.

In addition to the aboveedescribed methods of wet application oflLN'ephthal lhydrazines, we can prepare compositions'in which our mateials are extended in talc, clay or othersolid diluents which impart asurface contacting effect. Such formulations have particular utility inthe treat ment of seeds, wherein an aqueous application may promotepremature germination, or where a solvent application may damage theseed. For certain field 1010 applications we also prefer a dustformulation wherein a wet application might introduce certain secondaryeifects which are undesirable. Further specific examples of such typicalinert solid carriers which can be employed as diluents in our dustformulations include fullers earth, Ffyrophillite, Attaclay and theFiltrols.

Further, we can employ a combination of the above methods of applicationof our fungicides, hus, we can incorporate a surface-active agent orlubricant in our dust formulations, not only to ensure a uniform drymixture, but also to .enh l h spr ad n chara t r stics on l -p cation- QPa cu a u lit fo such formula.-

tions are the alkyl or alkylaryl sulfonate detergents. Likewise, asolvent formulation can be employed along with water, or Water and asurface-active agent. Such surface-active agents can be chosen, forexample, from the types represented by Triton X-100, SharplesNon-Ionic-218" or Tween. To illustrate, we dissolve N,N-phthalylhydrazine in a solvent, suchv as ethyl acetate, along with adispersant, and before application this concentrate is added to water,thereby producing a suspension of the fungicide in water, at the desiredconcentration for application.

In addition, to any of the above formulations we can incorporate anadherent or sticking agent or a humectant. Furthermore, the aboveformulations can be employed in admixture with other fungicidalmaterials or other biocides such as insecticides, larvicides,bactericides, vermicides, miticides, or with other materials which it isdesired to apply along with our fungicide, such as for exampleherbicides or fertilizers.

In addition to the free N,N-phthalylhydrazine, we can employ ourfungicides in the form of salts. Thus, for example, the alkali metalsalts, in par-. ticular the sodium and potassium salts, possess thecharacteristic of high water-solubility, and for some applications thisis preferred. Likewise, the alkaline-earth metal salts, including thecalcium, barium and magnesium salts, may be preferred for certain useswherein a more limited water solubility is desired. Other metal saltscan also be employed and can be chosen so as to impart not only aparticular water solubility but also to enhance the fungitoxicity of theN,N'- phthalylhydrazine. Examples of such embodiments of the fungicidesof our invention include the group 1 metal salts, as for example thecop-- per and silver salts; the group II metals, in particular zinc andmercury; the group IV metals, as for example tin and lead. Other metalsalts of N,N-phthalylhydrazine which are particularly effective includethe chromium, cobalt and iron salts thereof. One method of utilizing thesalts of our fungicides comprises applying a water solution thereof to afibrous or absorbent material to be protected, and thereafter depositingthe free azinedione upon the fibers thereof by treatment with a mildlyacidic material. One special technique which is particularly effectiveis to precipitate an aluminum lake of our fungicides upon fibrousmaterials, by methods which are well-known in the dye application art.

In addition to metal salts, N,Nphthalylhydrazine forms salts withorganic bases, the most common of which are the nitrogen bases, and inthis form our azinediones are particularly effec- 1 tive. Examples oforganic bases which are reacted with N,N-phthalylhydrazine to formactive fungicides include the alkylamines, such as methylamine,diethylamine, triethylamine, ethanolamine, diethanolamine,triethanolamine, ethylenediamine, morpholin'e, piperidine, pyridine,quinoline, n-butylamine, isoamylamine, dihexylamine, N-methyl Nbutylamine, triamylamine and benzylamine, and the arylamines, such asaniline, methylaniline, dimethylaniline toluidine, N-methyltoluidine,Xylidine, N-butylxylidine, a-naphthylamine, and B-naphthylamine.Likewise, ammonia itself forms ammonium salts withN,N'-phthalylhydrazide to form an effective, water-soluble fungicide.

We have illustrated the utility of N,Nphthalylhydrazine and the metalsalts thereof as fungitoxic materials by determining the concentrationat which the germination of 50 per cent of the spores of each of thefungi Alternarza cleracea. and .S'clerotinza fructz'cola is inhibited.The former is responsible for the potato blight, while the latter causespeach rot. These fungi are representative of fungus types which areresponsible for heavy crop damage. The ability to control these fungi isa reliable indication of the general applicability of our fungicides toprotect these and other important agricultural crops. These tests wereconducted as follows: parts of N,N'-phthalylhydrazine was trituratedwith 1,000 parts of distilled water containing one part of thecommercial dispersant Triton X400. This standard suspension wasthereupon further diluted with distilled water and the concentration atwhich one-half of the fungi contained in a drop of water on a microscopeslide were prevented from sporilating was determined. With the insolublemetal salts as for example the barium, zinc, mercury, lead or cobaltsalts, a similar procedure is employed, as well as with salts of mostorganic bases. With the soluble salts, as the sodium and potassium saltsof N,N'- phthalylhydrazine and ammonium and soluble organic-base salts,it is only necessary to form a standard solution of the fungicide inwater, and further dilute the solution to the minimum effectiveconcentration. For example against A. cleracea the effectiveconcentration of N,N'-phthalylhydrazine was less than 1 p. p. m. Thesalts are likewise efiective at similar concentrations. Our fungicidesare effective against S. fmcticola at a concentration of less than 10 p.p. m. This standard slide-germination method is described by theCommittee on Standardization of Fungicidal Tests of the AmericanPhytopathological Society in Phytopathology, 33, 627 (19%3).

We have established that the fungicides of our invention are non-toxicto seeds and seedlings by incubating cucumber and rye seeds at atemperature of 25 C. in the dark for four and seven days, respectively,in Petri dishes containing a filter paper moistened with aqueoussuspensions of our azinediones. Suspensions of our materials wereprepared by dispersing one part of the N,N-phthalylhydrazine orinsoluble salt thereof, or dissolving one part of the soluble salts, in10,000 parts of water containing 0.1 part of Santomerse-S, thusproducing a formulation containing 100 p. p. m. of active ingredient. Atthe end of the incubation period we compared the growth of the primaryroot tip of the cucumber seed and the growth of the rye coleop'tile"with that obtained on seeds incubated with distilled water. We found nosignificant inhibition, compared with the controls, when germinationproceeded in the presence of our fungicides. Germination of the treatedseeds was as complete as the control.

It is important that a fungicidal composition does not cause damage tothe leaves, stem, blossom, or fruit of a plant to which it is applied.When we dipped the entire'leaf of each of corn, soybean, tomato,cucumber and cotton plants in a suspension of N,N'-phthalylhydrazine ata concentration of 10,000 p. p. m., we observed no effect on theso-treated plants or upon the leaves which were dipped. In like fashion,when leaves aredipped in suspensions or solutions of salts of ourfungicides, no damage occurs to the plant. These dispersions were madeaccording to the procedure of the previous example. Furthermore, each ofthese plants was totally sprayed with dispersions of our fungicides inWater at a DISEASES OF FRUITS Apple scab Venturia inaequalis Peach andcherry rots. Scleroti'nia fructicola Pear blight Erwinia amyloz oraStrawberry leaf spot Mycosphaerella fragaria Cherry leaf spot.Coccomyces hiemalis Citrus scab Elsinoe fawcettic Citrus stem end rotDiaporthe citri DISEASES OF GRAINS Wheat stem rust Wheat leaf rust Oatcrown rust Sweet corn smut Rice brown spot Puccim'a gmmminis Puccz'm'atritz'cz'na Puceim'a coronata Ustz'lago zeae Hel'minthosporium oryzaeDiplodia zeae Corn rot (libberella zeae ll jusiirium monilifor'me stiago avenue Oat smut Ustilago Zevis DISEASES OF TUBE RS Fusarz'um botatisSweet potato Stem rot Fusarium hyperozysporum Potato late blightPhytophtho a infestans Sugar beet leaf spot Ceroospora beficola Sweetpotato black rot Ceratostomella fimbriata Potato Rhizoctoniose.

Rhizoctonia solam' Potato Scab Acfinomyces scabies MISCELLANEOUS VEGETABLE CROP DISEASES Tomato early blight Igiltgmaria solam' p anomycessp. Pea root and stem rots... "b Sp I Tomato septorla blight" Septonalycopersicz Peanut leaf spot C'ercospora per-sonata Celery late blight.Septoria apii Cabbage black leg Phoma Zingam Oueurbits down mildew.Peronoplasmopcra cubensz's MIS CE LLANEO US Cotton wilt Fusarium f 'mCotton root rot Phzlmatotrichu'm omnivorum Rhizoctonia solam' Cottonblights and boll rot Sclerotiu'm batatz'cola Diplodz'a gossypina Tobaccoblue mold Peronospom tabacimz Tobacco wild fire Phyto'monas tabacum Asone example of a method of formulating a dust containing our fungicides,we ground 100 parts of N, N -phthalylhydrazine with 1900 parts of talcsuch that the particles in the formulation were smaller than 80mesh,'and the concentration of active ingredient was per cent. Likewise,when the salts of this material are ground with talc, similar dustformulations are produced.

We prepared oil-in-water emulsions of our fungicides as follows: asaturated solution of N, N '-phthalylhydrazine in kerosene was added,with agitation, to water containing a small amount of Triton X-100, thusobtaining a dispersion suitable for application as a spray. In a similarfashion a dispersion is made of the oilsoluble salts thereof. For theoil-insoluble, water-soluble salts we reverse the above procedure.

It is evident from the foregoing that our fungicides can be firstformulated into a concentrate, wherein an inert diluent is admixedtherewith, and finally diluted to an appropriate concentration forapplication with the same or different diluent. Such final formulationwe prefer to employ between about 1 and 1000 p. p. m. of activeingredient. In general, from practical considerations, we prefer toprepare a concentrate containing up to approximately 50 weight per centof our fungicides. If preferred, however, our fungicides can be dilutedto application strength all at once. In either case, our fungicides whenincorporated in the diluent are stable on storage and can besatisfactorily handled in either the diluted or concentrated state.

The fungicides of our invention also protect other materials besidesplants and seeds. EX- amples of such materials, which are susceptible toattack by fungus organisms and which are protected by treatment withN,N'-phthalylhydrazine, or salts thereof, include wood, cloth fabrics,leather, fur, hair, feathers, felting painted or otherwise coatedsurfaces, and other articles of manufacture which comprise organicmaterials or are coated with such organic materials. O-ur fungicides canbe applied to such materials as sprays, dusts, or clips, or can bebrushed on, depending on the particular characteristics of the articleor material which it is desired to protect from fungus attack.Furthermore, our fungicides are useful as soil disinfectants and can beapplied directly thereto, thus providing protection to seeds, roots andemergent seedlings, or other material embedded in soil, such as forinstance wood, cloth or other articles from soil-infesting fungi.

Other methods of employing the fungicidal compositions of our inventionand other materials which can be protected from attack by fungusorganisms will be apparent to those skilled in the art and the abovespecific examples are intended only to illustrate our invention.However, we do not intend that our invention be limited to thesespecific examples.

We claim:

1. A fungicidal composition consisting essentially of a materialselected from the group consisting of N,N'-phthalylhydrazine, metallicsalts thereof and salts thereof with organic nitrogen bases in amountless than about 50 per cent by weight, an inert diluent and asurface-active agent.

2. A fungicidal composition consisting essentially of a materialselected from the group consisting of N,N-phthalylhydrazine, metallicsalts thereof and salts thereof with organic nitrogen bases in amountbetween about 1 and 1000 p. p. m., a diluent therefor and asurface-active agent.

3. The composition of claim 2 wherein the fungicidal ingredient isN,N-phthalylhydrazine.

WALDO B. IJGE'I'I'. REX D. CLOSSON. CALVIN N. WOLF.

References Cited in the file of this patent UNITED STATES PATENTS NameDate La-dd Oct. 14, 1947 OTHER REFERENCES Number

1. A FUNGICIDAL COMPOSITION CONSISTING ESSENTIALLY OF A MATERIALSELECTED FROM THE GROUP CONSISTING OF N,N-PHTHALYLHYDRAZINE, METALLICSALTS THEREOF AND SALTS THEREBOF WITH ORGANIC NITROGEN BASES IN AMOUNTLESS THAN ABOUT 50 PER CENT BY WEIGHT, AND INERT DILUENT AND ASURFACE-ACTIVE AGENT.